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Cobaltite-Gersdorffite Solid Solution As a Primary

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Cobaltite-Gersdorffite Solid Solution As a Primary 503 Thz Canadian M inerala g i st vol. 34,pp. 503-512 (1996) COBALTITE-GERSDORFFITESOLID SOLUTION AS A PRIMARYMAGMATIC PHASE IN SPESSARTITE, LACAUNEAREA, MONTAGNE NOIRE, FRANCE DIDIER BENAT, PIERREMONCHOIIX ANDFRANCIS TOLLON Leboratoire de Minzralogie et Cristallographie, UMR 5563, UniversitC Paul Sabatier, 39, AIIdes Jules Guzsde, 31000 Toulouse Cedex, France AssrRAc"r A cobaltite-gersdorffitesolid solution occursin spessartitesills from the l,acaunearea, Montague Noire, southemFrance, enclosedwithin phenocrystsand found in the matrix. It commonly enclosesrounded grains of pyrrhotite with lamellae of pentlandite.Compositional variation of cobaltite-gersdorffiteois representedmafuly by a Co-for-(Ni + Fe) substitution;the core is cobaltjferous,and the rim, nickeliferous.Atomic proportionsin the structuralformula as obtainedfrom over 80 analyses, vary witlin the following ranges:(Co6.s5-o5y'.{ie.27-a.66Fes.1o-a.3)As6.e7-1.67S0.se-o.sz. The Ni/Fe value is near 2, which could indicatethe presenceof a (1.{io.*Feo.u,)Aiscomponent witl a Ni-Fe order in the Ni site. Textural evidenceand compositional data suppofi an igneous rather rhaa secondaryorigin. Cobaltite-gersdorffite* can crystallize by separationof an early immiscible sulfaxsenideliquid from a calc-alkalinelamprophyric magma. These sills could representan atffactivetarget for Au prospectingin the MontagneNoire area. Kewords: cobaltite,gendorffite, solid solution,pdmaxy, spessartite, Montagne Noire, France. SoMlr,tans Une solution solide de cobaltite-gersdorftitese rencontredans un sill de spessartitede la r6gion de Lacaune,Montagne Noire, partie sud de la France, soit inclus dans les phdnocrisaux, soit dans h pate. Ce mindral renferme fr6quemmenten inclusion des grains arrondis de pyrrhotite avec des lamelles de pentlandite.Sa variation en composition est repr6sent6e essentiellementpar une substitution Ce-(I.{i + Fe), avec un coeur cobaltif?re et une bordure nick6lifbre. l,es formules structurales, obtenues i partir de 80 r6sultats d'analyses, varient dans les intervalles suivants: (Coo.os+.ssl.{h.zz+.66Fee.1an3)Ass.gr_r.o:So.:g_o.s7. I,e rapport NilFe est toujours voisin de 2, ce qui pourrait indiquer I'existence d'un Comfosint (Nh.orFq.::)AsS avec mise en ordre de Ni et Fe sur le site Ni. l€ur compositionet leur relation avec les ninerauiprimaires riigmatiques indiquent qu'ils sont le r6sultal d'un processusign6 plut6t qu'hydrothermal.Les solutions solidescobaltite-gersdorfftte cristalliseraient i partir d un liquide sulfo-ars6ni6,s6par6 pr6cocement par immiscibilit6 du magma lamprophyriquecalco-alcalin. Ces sills de spessartitepeuvent repr6senter une cible intdressantepour la prospectionde I'or en MontagneNoire. Mots-cl6s:cobaltite, gersdorffite, solution solide,primaire, spessartite,Montagne Noire, France. Ir.rrRooucilolI unusualoccurence will be usedto discusstheir origin: is the cobaltite-gersdorffrte,, a primary magnatic The occurrence of cobaltite-gersdorffite solid- phaseor a hydrothermalphase? solution in basic and ultrabasic rocks is generally consideredto be of hydrotherrnal oigtrn (Oen et al. Ttn Hosr SpsssARTrE 1971,Penuk et al. 1971,Oen 1973,Besson & Picot 1975, Leblanc 1986, Gervilla 7990, kfchard et al. The cobaltite-gersdorffrte* occurs in spessartite 1994). Occasionally,lamprophyric rocks may contain emplacedin Lower Cambriancarbonate formations in primary magmatic sulfides, generally pyrrhotite, the Lacaune area, Montagne Noire, southemFrance. pentlandite and chalcopyrite (Grosser 1966, Rohde B6aat et al. (1993) have described the geology, lglZybut magmaticco6altite-gersdorffite* has never mineralogy and geochemistryof the host spessartite, beenreported. and proposedthatit couldhave beenderivedby partial In this paper,we report new information (composi- melting of a metasomatically enriched garnet + tional variatiols s1d 26ning) on sulfarsenideminerals pblogopite t amphibole lherzolite. The water-rich found in sills of spessartitefrom the Lacaune area, nature of the magma is clearly indicated by the Montagne Noire, in soutlern France. Features of presence of hydrous mafic phenocrysts and by 5M TIIE CANADIAN MINERALOGIST plagioclase occurring only in the groundmass(c/. mica, quartz and apatite. Ocelli of light brown mica, Burnham1979, Nlan & Carmichael1984). commonly including microcrystals of cobaltite- Spessartitebelongs to the calc-alkalinesuite. It gersdorfflte., in their core, also are found. These containsamphibole (magfresio-hastingsite to pargasite) ocelli are interpretedas the product of transformation and phlogopite as phenocrysts, both commonly of relict olivine phenocrystsduring the ascentof the including microphenocrystsof chromianrutile, zrncian magma. chromite and cobaltite-gendorffite"., with occasional A very subordinate,secondary assemblage,with inclusionsof pyrrhotite. However,sulfarsenide-sulfide colorless amphibole, talc, chlorite, white mica, grains and oxide grains occur in separateinclusions. carbonateand pyrite, is found only near the veinlets The groundmasscomprises plagioclase, light brown within the fresh rock. Fto. 1A. Photomicrographsof grain of Ni - Co - Fe sulfarsenide.Secondary electron image of a subhedral grain of cobaltite-gersdorffiteoand correspondingNiKo, CoKo and FeKcrmaps showing an oscillatory zonation. PRIMARY COBALTITE-{ERSDORFFITE. MONTAGNE NOIRE s05 Conar-rnr-GnnsDoRFFTTEss and Co, CuFeS2for Cu, Fe and S, FeAsSfor As, and Sb2S3for Sb. The data were corrected using PAP Mineralogy and textures (SX50) procedures.Concentrations of major elements are accurateto x.1wtvo of the elementpresent, whereas The average spessartitecontains less than 0.17o concentrationsof minor elementsate less accurate,but by volume of cobaltite-gersdorffite"r.It occurs as arereproducibleto *0.1 wt%o. inclusions50 to 250 pm acrosswithin amphiboleand, Representative compositions of cobaltite- more rarely, within phlogopite phenocrysts,in the gersdorffrte.,and sulfides are given in Table 1. The ocelli of light brown micA and also in the matrix. cobaltite-gersdorffite., is a solid-solution series The grains of cobaltite-gersdorffite* appear white, between (Ni,Fe)-rich cobaltite and gersdorffite. with high reflectance and weak anisotropism.They Compositional ranges of Co, Ni, Fe, As and S, as occur as euhedral to subhedral single crystals obtained from 80 analyses (Fig. 2), are @gs. 1A, D) or in small aggregatesand, more rarely, (Cos.e5-a.5el'{is.n 4.66F eo.v+.3)Ase.y-r.s7Se.se-o.rr. as subsphericalgrains (Fig.lB). No evidence of Sb contentsinvariably arelow (maximum0.5 wtVo). exsolutionis visible, even at 500x magnificationwith Sb enters the cobaltite-gersdorffiless structure by the scanning electron microscope,in secondary- substitutionfor S (Fig. 3). As shown in Figure 4, the electron images (Figs. 1A, C). The crystals of degree of substitution of As for S increaseswith cobaltite-gersdorffrte*occasionally contain amphibole increasing(Ni + Fe) contents,in agreementwith the and phlogopite crystals as inclusions, as well as experimentalresults of Maurel & Picot (1974). rounded grains of pyrrhotite with lamellae of Dependingupon the silicate assemblagein which pentlandite(Frg. 1C). they occlu (phenocryst$, ocelli, groundmass), cobaltite-gersdorffite., shows distinct compositions Mineral chemistry (Frg. 2). The grains in the groundmassare Sb-poorto Sb-bearinggersdorffite (0.13-{.50 fi7o), with a As/S More than eighty elecuon-microprobe analyses value greaterthan 1.06.They are poorly zoned,with a were doneusing a CAMEBAX SX50 at the Laboratory core slightly more Co-rich than the rim (anal. 5 and 6, of Mineralogy, Toulouse (beam current of 20 nA, Table 1). The grains trappedin the phenocrystsor in 25 kY, with a counting time of 10 s at the peak the ocelli of light brown mica generally exhibit a positions and 5 s for symmetricalbackgrounds). The normal and discontinuouszonation between a large following standardswere used: pure elementsfor Ni core of Sb-poor, (Ni,Fe)-rich cobaltite with an As/S value less than 1.06 and a narow rim of gersdorffite (Frg. lD, anal. I to 3 in Table 1). More rarely, they exhibit, in addition, a nturow externalrim that is more cobaltiferous than gersdorffite, or even oscillatory zonation (Frg.lA). The maximum variation (e.g., anal. la to ld in Table 1) is as wide as the intergrain variation. The solvi in the systemNiAsS - CoAsS - FeAsS have been experimentally determined by Klemm (1965). There is complete miscibility between gersdorffite and cobaltite above 550oC. On the contrary, miscibility between arsenopyrite and cobaltite and betweenarsenopyrite and gersdorffiteis limited, particularly at low temperatures,because of differences in the crystal structureso pseudo- orthorhombic for arsenopyrite, pseudocubic for cobaltite and gersdorffite (Permingeat1991). As Ftc. 18. Photomicrograph of subspherical grain of cobaltite-gersdorffite*. 506 TTIE CANADIAN MINERALOGIST FIc. lC. Photomicrographsof grain of Ni - Co - Fe sulfarsenide.Secondary electron image of cobaltite- gersdorffite* crystal including phlogopite(Ph) and pyrrhotite(Po) with lamellaeof pentlandite(Pn), and correspondingNiKo, CoKoand FeKcl maps. shown in Figure 2, our compositions of cobaltite- different types of As-S ordering @ayliss 1982b).For gersdorffitessplot, with few exceptions,in a region that cobaltite,only thePca2l stucture ha$been determined would be in a single-phasefield at 500'C, and thus (Bayliss 1982a). Bayliss invoked a chemical reason suggestthat crystallization occurredat high tempera- to explain the order of As and S: "Since Fe (acid)
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